Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032977/bx2098sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032977/bx2098Isup2.hkl |
CCDC reference: 657714
The title compound was obtained (Stefanowicz, 2006) by the dehydratation of the glutaric acid in the acetic anhydride solution. The glutaric acid (30 g; 0,227 mol) was added to the 25 ml of the acetic anhydride. Obtained mixture was heated slowly until the boiling point was reached, and then refluxed for 15 minutes. Later the solvent was removed in a vacuo. Treatment of the obtained oil residue with naphthyl ether (200 ml) and later washing with the n-hexane resulted in the single crystals suitable for X-ray measurements. Glutaric anhydride undergoes the phase transitions, what was confirmed by the DSC technique. DSC studies on (I) disclosed two closely laying phase transitions at 154/183 K (cooling-heating) and 172/192 K. These phase transitions characterized by a significant temperature hysteresis may be classified as discontinuous ones. They are accompanied by a relatively small entropy effects: ΔS = 0.36 J/(mol K) and 0.20 J/(mol K).
The structure was solved by direct methods with using SHELXS97. The H atoms were placed in the idealized positions as riding on their parent atoms with distances of 0.98 Å with Uiso(H) values of 1.2Ueq(C). Although the molecule is achiral, the structure possesses a polar axis. The absence of atoms, which possess the atomic number higher than silicon causes that no anomoulus dispersion is observed. The Flack [(1983). Acta Cryst. A39, 876–881] parameter is meanigless in this case. The absolute direction of the polar axis was assigned arbitrarily and the Friedel pairs were merged before the final refinement.
The title compound (I) (Fig. 1) and some of its derivatives are commonly used as reagents in the organic synthesis (Freer et al., 1988; Takahashi et al., 2004). Several papers concerning the crystal state studies of glutaric anhydride derivatives, as 3-phenyl-1-oxacyclohexane-2,6-dione or β-chloroglutaric acid anhydride are available in the literature (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982), but surprisingly the crystal structure of the glutaric anhydride has not been determined yet.
This paper reports the crystal state studies of the glutaric anhydride. Compound I crystallizes in the i>P212121 space group with one independent molecule in the asymmetric unit.
The C1=O3 and C5=O2 bond lengths of 1.197 (3) Å and 1.188 (3) Å, respectively, remain in good agreement with those C=O bond lengths observed in related compounds crystal structures (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982; Qian et al., 2006). The differences in the C=O bonds lengths existing between discussed structures are similar to those observed for two independent molecules of β-chloroglutaric acid anhydride (Koer et al., 1972) and can be justified by the different intermolecular interactions, present in the crystal network. The C1—O1—C3 angle of 124.5 (2)° remains also in agreement with the numerous literature data (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982; Bertolasi et al., 1997; Qian et al., 2006). The six-membered ring of glutaric anhydride molecule adopts nearly envelope conformation, what is confirmed by the values of puckering parameters: q2 = 0.375 (2) Å, q3 = 0.251 (2) Å and ψ2= 174.5 (4)° (Cremer & Pople, 1975) for the O1/C1/C2/C3/C4/C5 ring atom sequence. The O1, C1, C2, C4 and C5 atoms are coplanar (r.m.s. deviation = 0.0188), and C3 carbon is deviated from the plane defined by above atoms by -0.625 (4) Å.
In glutaric anhydride crystal structure no hydrogen bonds are observed. Only very weak interactions as C—H···O contacts between adjacent molecules can be recognized (Table 2). Molecular packing (Fig. 2), which exists in the glutaric anhydride crystals can explain the low value of the melting point.
For related literature, see: Bertolasi et al. (1997); Bocelli & Grenier-Loustalot (1982); Cremer & Pople (1975); Freer et al. (1988); Koer et al. (1972); Qian et al. (2006); Stefanowicz (2006); Takahashi et al. (2004).
For related literature, see: Burnett & Johnson (1996); Farrugia (1997).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP (Bruker, 1999); software used to prepare material for publication: SHELXL97.
Fig. 1. ORTEP atom numbering scheme of I. The thermal ellipsoides were drawn at 20% probability. | |
Fig. 2. The view of the packing of I, viewed along the a axis. Atom O2 is at (1 - x,-1/2 + y,3/2 - z). |
C5H6O3 | F(000) = 240 |
Mr = 114.10 | Dx = 1.413 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 668 reflections |
a = 5.410 (4) Å | θ = 3.1–28.5° |
b = 7.520 (6) Å | µ = 0.12 mm−1 |
c = 13.180 (8) Å | T = 240 K |
V = 536.2 (7) Å3 | Needle, colourless |
Z = 4 | 0.53 × 0.15 × 0.15 mm |
KUMA KM-4 CCD κ-geometry diffractometer | 668 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 28.5°, θmin = 3.1° |
ω and φ scans | h = −7→5 |
3600 measured reflections | k = −9→10 |
774 independent reflections | l = −17→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.0184P] where P = (Fo2 + 2Fc2)/3 |
774 reflections | (Δ/σ)max < 0.001 |
73 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.11 e Å−3 |
C5H6O3 | V = 536.2 (7) Å3 |
Mr = 114.10 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.410 (4) Å | µ = 0.12 mm−1 |
b = 7.520 (6) Å | T = 240 K |
c = 13.180 (8) Å | 0.53 × 0.15 × 0.15 mm |
KUMA KM-4 CCD κ-geometry diffractometer | 668 reflections with I > 2σ(I) |
3600 measured reflections | Rint = 0.034 |
774 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.22 e Å−3 |
774 reflections | Δρmin = −0.11 e Å−3 |
73 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5092 (2) | 0.6331 (2) | 0.60650 (11) | 0.0495 (4) | |
C1 | 0.5835 (4) | 0.5529 (3) | 0.51710 (16) | 0.0471 (5) | |
O3 | 0.4401 (3) | 0.5620 (2) | 0.44814 (12) | 0.0712 (6) | |
C2 | 0.8311 (4) | 0.4690 (3) | 0.51408 (16) | 0.0504 (5) | |
H2A | 0.9512 | 0.5552 | 0.4880 | 0.060* | |
H2B | 0.8270 | 0.3681 | 0.4671 | 0.060* | |
C5 | 0.6538 (4) | 0.6438 (3) | 0.69384 (16) | 0.0517 (5) | |
O2 | 0.5715 (4) | 0.7309 (3) | 0.76100 (13) | 0.0813 (7) | |
C4 | 0.8970 (4) | 0.5521 (3) | 0.69368 (16) | 0.0530 (5) | |
H4A | 0.9273 | 0.5026 | 0.7613 | 0.064* | |
H4B | 1.0269 | 0.6398 | 0.6799 | 0.064* | |
C3 | 0.9151 (4) | 0.4048 (3) | 0.61660 (17) | 0.0545 (6) | |
H3A | 1.0865 | 0.3634 | 0.6122 | 0.065* | |
H3B | 0.8121 | 0.3044 | 0.6381 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0396 (7) | 0.0576 (9) | 0.0512 (8) | 0.0085 (7) | 0.0013 (6) | −0.0010 (7) |
C1 | 0.0472 (10) | 0.0467 (10) | 0.0475 (10) | −0.0027 (10) | −0.0023 (9) | 0.0008 (9) |
O3 | 0.0670 (11) | 0.0888 (13) | 0.0577 (10) | 0.0057 (11) | −0.0200 (9) | −0.0027 (9) |
C2 | 0.0518 (12) | 0.0504 (11) | 0.0489 (11) | 0.0006 (10) | 0.0030 (10) | −0.0099 (10) |
C5 | 0.0465 (10) | 0.0605 (13) | 0.0479 (11) | 0.0054 (10) | 0.0058 (10) | −0.0034 (11) |
O2 | 0.0701 (12) | 0.1111 (15) | 0.0627 (11) | 0.0210 (12) | 0.0087 (10) | −0.0317 (11) |
C4 | 0.0471 (11) | 0.0664 (13) | 0.0455 (10) | 0.0088 (11) | −0.0034 (9) | 0.0005 (11) |
C3 | 0.0493 (11) | 0.0535 (12) | 0.0606 (12) | 0.0103 (10) | 0.0033 (11) | 0.0022 (10) |
O1—C1 | 1.383 (3) | C5—O2 | 1.188 (3) |
O1—C5 | 1.394 (3) | C5—C4 | 1.485 (3) |
C1—O3 | 1.197 (3) | C4—C3 | 1.506 (3) |
C1—C2 | 1.481 (3) | C4—H4A | 0.9800 |
C2—C3 | 1.505 (3) | C4—H4B | 0.9800 |
C2—H2A | 0.9800 | C3—H3A | 0.9800 |
C2—H2B | 0.9800 | C3—H3B | 0.9800 |
C1—O1—C5 | 124.43 (15) | C5—C4—C3 | 113.55 (18) |
O3—C1—O1 | 115.69 (19) | C5—C4—H4A | 108.9 |
O3—C1—C2 | 126.2 (2) | C3—C4—H4A | 108.9 |
O1—C1—C2 | 118.13 (17) | C5—C4—H4B | 108.9 |
C1—C2—C3 | 112.67 (19) | C3—C4—H4B | 108.9 |
C1—C2—H2A | 109.1 | H4A—C4—H4B | 107.7 |
C3—C2—H2A | 109.1 | C2—C3—C4 | 110.50 (18) |
C1—C2—H2B | 109.1 | C2—C3—H3A | 109.6 |
C3—C2—H2B | 109.1 | C4—C3—H3A | 109.6 |
H2A—C2—H2B | 107.8 | C2—C3—H3B | 109.6 |
O2—C5—O1 | 115.9 (2) | C4—C3—H3B | 109.6 |
O2—C5—C4 | 126.1 (2) | H3A—C3—H3B | 108.1 |
O1—C5—C4 | 117.99 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O2i | 0.98 | 2.53 | 3.353 (4) | 142 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C5H6O3 |
Mr | 114.10 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 240 |
a, b, c (Å) | 5.410 (4), 7.520 (6), 13.180 (8) |
V (Å3) | 536.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.53 × 0.15 × 0.15 |
Data collection | |
Diffractometer | KUMA KM-4 CCD κ-geometry diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3600, 774, 668 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.14 |
No. of reflections | 774 |
No. of parameters | 73 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.11 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP (Bruker, 1999), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O2i | 0.98 | 2.53 | 3.353 (4) | 142 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
The title compound (I) (Fig. 1) and some of its derivatives are commonly used as reagents in the organic synthesis (Freer et al., 1988; Takahashi et al., 2004). Several papers concerning the crystal state studies of glutaric anhydride derivatives, as 3-phenyl-1-oxacyclohexane-2,6-dione or β-chloroglutaric acid anhydride are available in the literature (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982), but surprisingly the crystal structure of the glutaric anhydride has not been determined yet.
This paper reports the crystal state studies of the glutaric anhydride. Compound I crystallizes in the i>P212121 space group with one independent molecule in the asymmetric unit.
The C1=O3 and C5=O2 bond lengths of 1.197 (3) Å and 1.188 (3) Å, respectively, remain in good agreement with those C=O bond lengths observed in related compounds crystal structures (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982; Qian et al., 2006). The differences in the C=O bonds lengths existing between discussed structures are similar to those observed for two independent molecules of β-chloroglutaric acid anhydride (Koer et al., 1972) and can be justified by the different intermolecular interactions, present in the crystal network. The C1—O1—C3 angle of 124.5 (2)° remains also in agreement with the numerous literature data (Koer et al., 1972; Bocelli & Grenier-Loustalot, 1982; Bertolasi et al., 1997; Qian et al., 2006). The six-membered ring of glutaric anhydride molecule adopts nearly envelope conformation, what is confirmed by the values of puckering parameters: q2 = 0.375 (2) Å, q3 = 0.251 (2) Å and ψ2= 174.5 (4)° (Cremer & Pople, 1975) for the O1/C1/C2/C3/C4/C5 ring atom sequence. The O1, C1, C2, C4 and C5 atoms are coplanar (r.m.s. deviation = 0.0188), and C3 carbon is deviated from the plane defined by above atoms by -0.625 (4) Å.
In glutaric anhydride crystal structure no hydrogen bonds are observed. Only very weak interactions as C—H···O contacts between adjacent molecules can be recognized (Table 2). Molecular packing (Fig. 2), which exists in the glutaric anhydride crystals can explain the low value of the melting point.